Y. K. Chau

Occurrence of organotin compounds in water and sediment in Canada

Abstract Water and sediment samples from 265 locations across Canada were analyzed for butyltin and methyltin species, and inorganic tin. In 10% of the water samples the highly toxic tributyltin species was found at concentrations which could cause growth retardation upon chronic exposure to a sensitive organism, rainbow trout yolk sac fry. High concentrations of tributyltin were found in some sediments (up to 10 mg Sn/kg dry weight), but the biological availability of sediment-associated tributyltin is unknown. Tributyltin was mainly found in areas of heavy boating and shipping traffic, which is consistent with its use as an antifouling agent in some paints for boats, ships and docks. The methyltin species were found much less frequently in water and sediment than tributyltin and its degradation products.

Evaluation of derivatization techniques for the analysis of organotin compounds in biological tissue

Abstract The two commonly used derivatization techniques for the speciation of organotin compounds in biological tissue, namely, (1) direct in situ derivatization with sodium tetraethylborate, and (2) tropolone extraction followed by derivatization with ethyl Grignard reagent, were evaluated and validated using a spiked tissue and reference fish tissue (NIES No. 11). Their applications in the analysis of real mussels are given.

Occurrence of butyltin compounds in mussels in Canada

The presence of the highly toxic antifouling agent tributyltin (TBT) and its degradation products was determined in four species of mussels collected from 34 locations in fresh water in Ontario and in sea water on Canadas west and east coasts. The purpose of the study was to establish baseline information in order to assess TBT trends in mussels after the 1989 Canadian regulation of antifouling uses of TBT. In fresh water, concentrations of TBT were much higher in zebra mussels (Dreissena polymorpha) than in Elliptio complanata or Lampsilis radiata radiata. High concentrations of TBT were also found in Mytilus edulus in sea water. Residues of TBT in all species were similar to those that have been determined in other parts of the world before and after the regulation of antifouling uses of TBT in various countries. Analyses for degradation products indicated that zebra mussels metabolize TBT at about the same rate as L. radiata radiata and M. edulis, but more slowly than E. complanata.

Physiological and biochemical responses of several freshwater algae to a mixture of metals

Abstract A mixture of ten metals (As, Cd, Cr, Cu, Fe, Pb, Hg, Ni, Se and Zn) at the Great Lakes Water Quality Objective levels was found to reduce the primary productivity of four cultured freshwater algae ( Scenedesmus , Chlorella , Anabaena and Navicula ) as well as natural phytoplankton from Lake Ontario water. The metal mixture also caused a reduction in the reproduction and transport of an amino acid analogue (α-aminoisobutyric acid) by Ankistrodesmus . The depuration and exchange of the amino acid analogue were not affected by the metal mixture. The nitrogenase activity of Anabaena was, however, reduced in the presence of the metal mixture.

Relationship between water solubility of chlorobenzenes and their effects on a freshwater green alga

The effective concentrations of benzene and 12 chlorobenzenes that reduced 50% of the primary productivity (EC50) of a freshwater green alga, Ankistrodesmus falcatus, were determined. Benzene was the least toxic chemical and the toxicity increased as the degree of chlorine substitution in the aromatic ring increased. No EC50 value could be obtained for HCB. A quantitative relationship was found to exist between water solubility, lipophilicity and the EC50. A good correlation was also observed between the EC50 for this alga and other toxicity data for various aquatic biota.

Determination of methylcyclopentadienylmanganese tricarbonyl (MMT) in gasoline and environmental samples by gas chromatography with helium microwave plasma atomic emission detection

A highly sensitive and specific method is described for the determination of methyl-cyclopentadienylmanganese tricarbonyl (MMT) in gasoline and environmental samples by gas chromatography-plasma atomic emission detection (GC-AED). The procedure is simple, rapid and free from interferences. The absolute limit of detection is 0.5 fg of MMT (0.5 x 10 -15 g) expressed as Mn. The precision for replicate injections (n=5) of an MMT solution (10 pg Mn) was 2.8% relative standard deviation (RSD). Applications of the method to analysis of gasoline (petrol), and preliminary results of the analyses of environmental samples such as air and roadside dirt, are given.

Occurrence of butyltin compounds in beluga whales (Delphinapterus leucas)

Fifty-two beluga whale samples (Six liver samples, and 46 blubber samples including ones from different depths of the fat layer) from the St Lawrence River, Canada, were analyzed for butyltin compounds (mono-, di-, and tri-butyltin) with a view to investigating the occurrence and contamination of butyltin in these animals. A special procedure was also developed for the determination of butyltin compounds in blubber samples with high lipid content (up to 95%). Total-butyltin concentrations in liver samples were found to be much higher than those in the blubber samples. The concentrations of butyltin compounds in blubber samples were observed to be related to their lipid content. Concentration levels of butyltin species in beluga whale were compared with those in other marine vertebrates in other parts of the world. The presence of butyltin compounds in liver and blubber samples suggests the accumulation of these toxicants by beluga whale.

Recent studies of residual tributyltin in coastal British Columbia sediments

Butyltin concentrations in the sediments of two coastal areas of British Columbia, Canada, are reported. Two recent box cores from the deepest basin in the Strait of Georgia were sectioned and analyzed by GC–atomic emission spectrometry. No butyltin compounds were detected above 0.5 μgSn kg−1 (dry weight) in either core. These results are compared to those for a previous (1991) core from the same area. In that study, tributyltin (TBT) concentrations were in the range 1–2 μgSn kg−1 down the core and were higher than those of either of the degradation products, dibutyltin (DBT) and monobutyltin (MBT). Radioisotope dating (210Po–210Pb counting methods) was used to establish the rates of sedimentation of 0.25 and 2.6 cm y−1 at the two sites. Data suggest that a combination of rapid deposition of new, less-contaminated material and degradation of previously deposited butyltin compounds has resulted in the observed absence. Thirty-three surface sediments from the northern BC coastal harbor at Prince Rupert, collected in 1995, were analyzed for butyltin residues by GC–FPD. Concentrations of TBT, DBT and MBT were in the ranges from below the appropriate limit of detection (LOD) to 1262, to 109 and to 37 μgSn kg−1, respectively. TBT/DBT ratios ranged from 0.2 to 62 with most above unity, indicating that there is continuing fresh input of TBT. The sources are almost exclusively large ocean-going vessels that use the harbor for long-term anchorage. These findings are discussed with reference to the global TBT status.

The relationship between tribuyltin (TBT) accumulation and toxicity to Hyalella azteca for use in identifying TBT toxicity in the field

The relationship between bioaccumulation and toxicity of tributyltin in Hyalella azteca was determined for future use in identifying freshwater sites of TBT induced toxicity in the field. Hyalella accumulated waterborne TBT rapidly, reaching equilibrium within 1 week. Short exposure times are, therefore, sufficient to measure TBT availability in laboratory or field exposures. Accumulation was not affected significantly by body size for animals between 0.1 and 0.6 mg dry weight, eliminating the need for a body size correction factor. Young amphipods were more sensitive to TBT than adults when both were exposed for 1 week. The 4-wk LC50 initiated with 0–1-week-old young was 4.8 nM. TBT accumulation was approximately proportional to TBT in water, and the 4-week LC50 expressed on a body concentration basis was 110 nmole/g dry weight. Accumulation of TBT by adult Hyalella to concentrations of about 100 nmole/g or more during short term (1-wk) exposures to environmental samples would suggest chronic TBT-induced toxicity is present at those sites.

A method for the analysis of butyltin chlorides in air by gas chromatography with atomic emission detection.

An initial screening test compared the use of tropolone (2-hydroxy-2,4-6-cycloheptatrienone) in acetic acid with sodium diethyldithiocarbamate (NaDDC) as chelating agents for the extraction of butyltin chlorides from glass fiber filters and XAD-2 resin tube. NaDDC was chosen for subsequent analyses. Mono-, di-, and tributyltin chloride were spiked onto glass fiber filters and XAD-2 resin, extracted in toluene with NaDDC and derivatized with pentylmagnesium bromide. Derivatized butyltin species were determined by gas chromatography with plasma atomic emission detection. Glass fiber filters and XAD-2 resin were found to provide high retention of butyltin compounds during sampling and efficient recovery of butyltin compounds by extraction with NaDDC.